Film-forming composition with a terephthalamide ester plasticizer



a 2,824,018 1C6 Patented Feb. is, 1958 United States Patent. 01

of the alcohol has been removed, usually 4 to 6 hours, 2 824 018 or the clear solution allowed to stand for about 12 hours at room temperature until the reaction product crystal- FILM-FORIVHNG COMPOSITIQN WITH A TEREPH. lizes. The product is then reacted with a dioyl chloride THALAMIDE ESTER PLASTICHZER to produce the corresponding ester. Any dioyl chloride.

Ral h T. K. Cornwall Rosemont Pa. assi nor to Amerlmay be used having a carbon Chan-1 length from 5 to c n Viscose Corpoi ation, Philadelphia, %a., a corporacarbon i Such pentaneqloyl chlondfi. hexane fion of Delaware dioyl chloride, heptanedtoyl chloride, octanedioyl chloride, nonanedioyl chloride, decanedioyl chloride, benzene- N0 Dfflwing- App y 1955 10 dicarbonyl chloride, cyclohexanedioyl chloride, naphsenal 525,350 thenedicarbonyl chloride,,the chloride of p-phenoxyacetic 4 Claims (CL acid, adipyl chloride, suberyl chloride, oxalyl chloride,

and the like. Aralkyl dioyl chlorides include the chlorides of methyl-, ethyl-, propyl-, butyl, amyl-, and hexyl- This invention relates to novel compositions of matter, benzenedicarboxylic acid.

more specifically, to the combination of a film-f0rming The following examples illustrate preferred method polymer, natural or synthetic, with a terephthalamide for the preparation of terephthalamide derivatives conester as a plasticizer. This application is a continuationtemplated by the present invention.

EXAMPLE I Adipate of N,N'-bis-(beta-hydroxyerhyl)-terephthalamide in-part of my application Serial No. 333,616, filed Janu- N,N'- bis -(beta-hydroxyethyl)- terephthalamide (5 g.,

ary 27, 1953, now abandoned, which in turn is a con- 0.02 mole) was dissolved in 135 cc. pyridine at a slight tinuation-in-part of my application Serial No. 135,835, boil. Adipyl chloride (2.4 g., 0.013 mole) wasadded filed December 29, 1949, now abandoned, which in turn slowly over a period of 1 /2 hours. Refiuxing was conis a continuation-in-part of my application Serial No. tinned for another half hour. One cc. of water was 75,965, filed February 11, 1949, now abandoned. added to the reaction mixture to take care of the pyridine The terephthalamide ester component of the present hydrochloride formed, and the mixture was then poured invention is formed by the reaction of a dioyl chloride into 700 cc. cold toluene. Brown crystals were recovwith N,N-bis-(beta-hydroxyethyl)-terephthalamide. The ered on chilling in an icebox. The crystals were recryscompounds may be represented by the following generic tallized from boiling ethanol using decolorizing Darco.

formula The final product, which had a faint purple cast to the u u u Ii ii i (B--O-CR OC2H4)( )r-nN-C-OC )r-n(G2H4-O''CR--OB)n wherein n is an integer having a value from 1 to 2, R is crystals, was obtained in 64.5 percent yield. It yellowed a divalent radical selected from the group consisting of at 160 C., browned at 190 C., and melted at 216 C. alkyl, aryl, alicyclic, and aralkyl radicals having a chain The product, C H N 0 analyzed as follows: length of from 3 to 12 carbon atoms and B is selected Theor C, 58.80; H, 6.19; N, 8.61 from the group consisting of hydrogen and Foundy: C 5679; H 701; N, 8.77

i1 ii The product was insoluble in water, acetone, n-heptane, T O T toluene, benzene, cyclohexane, ethyl acetate, and ethyl. (Inn, H ether. It was soluble in pyridine and hot ethanol and wherein x is an integer having a value from 1 to 2. butanol These compounds have been prepared and found to EXAMPLE H vary from white crystalline solids to brownish resinous p (acid phthalate) of N,N' b,-s (betwhydroxyethyl)- substances and are useful as intermediates in the producterephthalamide tion of synthetic resins and fibers and as plasticizers for 0 high polymers. H

These esters may be prepared as follows: mono- 0 ethanolamine or di-ethanolamine is heated with a terephn l thalic acid or acid ester such as diethyl terephthalate in O NHO"H4 O ethyl alcohol until a clear solution of the reactants is obtained. The reaction product, N,N'-bis-(beta-hydroxyethyD-terephthalamide or N,N-tetra-(beta-hydroxyethyD- terephthalamidais removed from the solution and further reacted with a dioyl chloride to produce the corre- 11 sponding ester thereof. For example, the mixture of 0 reactants methyl alcohol may be heated until the clear The terephthalamide, N,N'- bis -(beta-hydroxyethyl).- solution is obtained and the heating continued until all terephthalamide (5 g., 0.02 mole), was dissolved in cc. of pyridine at a slight boil. (6 g., 0.041 mole) dissolved in 35 cc. of pyridine was added Slowly over a period of 2 /2 hours. Refiuxing was continued for another half hour. The pyridine was then distilled off under vacuum until the temperature started to rise. The viscous brown material remaining was placed into 500 cc. of hot toluene which was then cooled. The brown semi-solid material recovered was dissolved in hot pyridine which was then placed in ice water. The light tan crystals recovered turned yellow at 105 C. and melted at 230 C. The product, C H O N analyzed as follows:

Theory: C, 61.50; H, 4.41; N, 5.09

Found: C, 63.31; H, 4.58; N, 4.56

The product was insoluble in water, ethanol, acetone,

n-heptane, toluene, benzene, chloroform, cyclohexane, 1,4-dioxane, ethyl acetate, and ethyl ether. The compound was slightly soluble in hot chloroform and completely soluble in hot pyridine.

EXAMPLE III O A-OH (ti-H The terephthalamide, N,N'-tetra-('beta-hydroxyethyl)- terephthalamide g., 0.029 mole), was dissolved in 75 cc. of pyridine. Phthalic anhydride (17.5 g., 0.118 mole) dissolved in 50 cc. of pyridine was added slowly over a period of 1 /2 hours and refluxing was continued for an additional hour. The reaction mixture was placed into 1 liter of cold toluene. The oil that separated out was Washed repeatedly with cold water and hot ether. A brown resin-like material with a softening point of 104 C. was obtained. The compound was insoluble in water, ethanol, acetone, n-heptane, benzene, toluene, chloroform, 1,4-dioxane, cyclohexane, ethyl acetate, and ethyl ether. It was slightly soluble in hot acetone, benzene, toluene, and chloroform and soluble in hot pyridine.

The esters described above are preferably used as plasticizers and coating agents for cellulosic films and sheets. For example, they may be employed as the plasticizer in moistureproofing and/or heat-sealing coatings for cellophane, such as those described in my Patents 2,487,105 and 2,487,106. Other film-forming materials which may be plasticized by the dipropionate of the present invention include 1) thermoplastic resins such as polyvinyl chloride, polyvinylidene chloride, polystyrene, copolymers of vinyl chloride and vinyl acetate, copolymers of methyl methacrylate and vinyl chloride, polyvinyl butyral, polyvinyl acetal, polymethyl methacrylate, polymethyl acrylate, polyethylene, polyamides, natural rubbers, synthetic rubbers; chlorinated rubber, polysulfides, polyisobutylenes, cyclized rubber, rubber hydrochloride, buna rubber, coumarone-indene with rubber, oil-modified and unmodified alkyd resins prepared from dihydroxy alcohols and dicarboxylic acids, phenol-formaldehyde resins prepared from phenols having only two reactive positions, (2) thermoplastic cellulose compounds such as cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose propionate, benzyl cellulose, ethyl cellulose, butyl cellulose, hydroxyethyl cellulose, cellulose nitrate, mixed esters or ether-esters such as cellulose acetate-nitrate, cellulose acetate-propionate or ethyl cellulose-nitrate, (3) such thermosetting resins as o-Phthalic anhydride urea-formaldehyde, phenol-formaldehyde (phenols having three reactive positions), melamine-formaldehyde, alkyd resins prepared from polyhydric alcohols and polycarboxylic acids, phenol-furfural, unsaturated polyesters, polyallyl alcohol and derivatives, protein-formaldehyde resins such as casein-formaldehyde and shellac-formaldehyde and (4) mixtures of thermoplastic and thermosetting resins such as polyvinyl chloride and urea-formaldehyde-butanol ether, polyvinyl chloride and phenolformaldehyde, polymethacrylate and urea-formaldehyde, polystyrene and alkyd, coumaroneindene and alkyd, polyvinyl acetal and melamine-formaldehyde. In such compositions, the film-forming material may be present in a proportion of 40 to by weight of the total solids in the composition, and the dipropionate of the present invention may be present in a proportion of 5 to 45% by weight of the total solids.

While it is an advantage of'the present plasticizers that they possess solvent powers for so many plastic components that they can normally be used as the only plasticizer, the invention is by no means limited to plastic compositions in which it is the only plasticizer present. On the contrary, it may be associated with other plasticizers such, for example, as dibutyl phthalate, dilauryl phthalate, cyclohexyl butyl phthalate, di(methylcyclohexyl) phthalate, di(dimethylcyclohexyl) adipate, dicycloheXyl adipate, tricresyl phosphate, esters of o-benzoyl benzoic acid such as butyl benzoyl benzoate derivatives of toluene sulfonamide, or the like.

As moistureproofing agents, Waxes or wax-like material such as paraffin, petrolatum, ceresin, japan wax, palm Wax, beeswax, certain chlorinated hydrocarbons, Chinese insect wax, or other synthetic waxes or Wax-like materials may be used. If some of these waxes are too soft for the purpose desired, they may be mixed with harder waxes of the group or with carnauba wax, candelilla wax or other harder waxes. Generally, parafiin serves as a satisfactory moistureproofing agent which may be hardened, if necessary, by admixture with carnauha Wax or candelilla wax.

In the preparation of moistureproofing coating conipositions comprising a cellulose derivative and a moistureproofing agent, it is advantageous to include some material Which will improve the compatibility of these two ingredients. This material is referred to as a blending agent and is usually of a resinous nature, although this is not absolutely necessary. When the blending agent is resinous, advantage may be taken of its film-forming characteristics, it any, and sufiicient quantity may be added to a coating composition to contribute towards the body and build of that composition in addition to the blending action. Depending on the nature of the blending agent, more or less plasticizing action on the cellulose derivative may be obtained.

As the blending agents, any of the natural or synthetic resins commonly available may be used so long as they are compatible and form homogeneous mixtures. Such resins may include ester gum, rosinates, hydrogenated rosin, hydrogenated rosin esters, dammar, copal, kauri, alkyd resins, vinyl derivatives, chlorinated diphenyl resins, and soluble resin of the phenol-formaldehyde type. Nonresinous blending agents may be used when they yield homogeneous mixtures and these may include hydrogenated castor oil, castor oil phthalate, lanolin or wool grease, ethyl abietate, methyl abietate, diethylene glycol rosinate, diethylene glycol hydrorosinate, or the like.

It is the most convenient to apply the above lacquer and moistureproofing coating compositions to base materials, such as sheets of regenerated cellulose, by means of suitable solvents. Thus, the film-forming ingredients may be dissolved to give a coating solution of an appro priate viscosity and solids content, whereupon the solution may be applied to the desired base in accordance with the methods known in the art. The solvents may be removed and the coated base subjected to an elevated 5 temperature at least equal to the melting point of the wax, whence, after cooling, a clear, transparent moisture proof, coated base will be obtained.

These moistureproofing compositions may be applied to various sheet material to produce wrapping tissues which are flexible, moistureproof and heat-scalable and which exhibit highly improved surface characteristics including excellent surface slip and resistance to caking, sticking, or marring during storage. A variety of base sheet materials may be used, such as cellulosic materials, paper, albuminous materials (gelatin, agar-agar, casein), or films made from rubber derivatives, that is, rubber hydrochloride, chlorinated rubber, or the material prepared by reacting rubber and a metal halide such as boron trifluoride, stannous or stannic chloride, stannic acid, and other materials. In the preferred embodiment of the invention, a non-porous, non-fibrous, dense, smooth surfaced, and preferably transparent material such as regenerated cellulose, cellulose ester films including cellulose nitrate and cellulose acetate, or cellulose ether films including ethyl cellulose, benzyl cellulose, glycol cellulose, or lowly etherified cellulose such as those in which there is only one substituent group for several glucose units of cellulose is employed.

6 EXAMPLE B Parts Nitrocellulose 45 Compound of Example II 22 Dibutyl phthalate 7.5 Paraflin, melting point 67 C Ester gum Blown rapeseed oil 0.5

One part of the composition was dissolved in 250 parts of the solvent containing 15 parts ethyl acetate, 15 parts butyl acetate and 70 parts toluene. The resulting mixture was applied as a coating to a sheet of cellophane and the sheet was allowed to dry. The resulting sheet was flexible and moistureproof.

It is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

I claim:

1. A composition of matter comprising (1) an organic plastic film-forming material selected from the group consisting of thermoplastic resins, thermoplastic cellulose esters and ethers, thermosetting resins, mixtures of thermoplastic and thermosetting resins and (2) as a plasticizer a compound having the formula In such compositions, the film-forming material may be'present in a proportion of 40 to 95 percent by weight of the total solids in the composition, and the esters of the present invention may be present in a proportion of 5 to 34 percent by weight of the total solids.

In the following examples using the esters of the present invention plasticizers are used as heat-sealing and moistureproofing lacquers for application to cellophane, the parts given are by weight.

EXAMPLE A Parts Nitrocellulose 50 The product of Example I 35 Parafiin, melting point 67 C 4 Ester gum l0 Blown rapeseed oil 1 One part of the above composition was dissolved in about 250 parts of a solvent mixture containing 15 parts ethyl acetate, 15 parts butyl acetate and 70 parts toluene. The solution was then applied as a coating to cellophane and dried in the usual way. The resulting sheet was moistureproof and remained flexible.

where n is 1 or 2, R is selected from the group consisting of alkyl, aryl, alicyclic, and aralkyl radicals having a chain length of from 3 to 12 carbon atoms and B is selected from the group consisting of hydrogen and References Cited in the file of this patent UNITED STATES PATENTS Cornwell Nov. 8, 1949 Jayne et a1. May 8, 1951 Ralph T. K. Cornwell It is hereby certified that error a numbered patent requiring correctio as corrected below.

Columns 1 and 2, lines 21 to of the formula reading column 2, lines 57 to 6 of as in the patent:

column 3, lines 25 to 35, Ex

of as m the patent:

Patent No. 2,824,018

UNITED @TATES PATENT OEFICE Certificate of Correction February 18, 1958 ppears in the printed specification of the ubovg n and that the said Letters Patent should rea 24, Example I, for the extreme right-hand portion I! read @C-IVHCzILOH 7, Example II, the formula should appear as shown below instead if C-OH Signed and sealed this 11th day of November 1958.

[SEAL] Attest KARL H. AXLINE,

Attestz'ng Oflicer.

ROBERT C. WATSON (Jammz'ssz'oner of Patents. 

1. A COMPOSITION OF MATTER COMPRISING (1) AN ORGANIC PLASTIC FILM-FORMING MATERIAL SELECTED FORM THE GROUP CONSISTING OF THERMOPLASTIC RESINS, THERMOPLASTIC CELLULOSE ESTERS AND ETHERS, THERMOSETTING RESINS, MIXTURES OF THERMOPLASTIC AND THERMOSETTING RESINS AND (2) AS A PLASTICIZER A COMPOUND HAVING THE FORMULA 